- He was cast as the leading man in V for Vendetta (2005) but departed halfway in, having had creative differences with the makers of the film.
- The name Purefoy is originally Norman French and literally means "good faith" or "my word or bond is in good faith." Some Purefoys went to England during the Norman Conquest, and others emigrated to England as French Huguenot expatriates in the 15th century.
- Screen tested for the Bond role in GoldenEye (1995).
- James' co-star in Rome (2005), Kevin McKidd, also played his love interest in Bedrooms and Hallways (1998).
- At boarding school, he once serenaded the girls at a nearby school with 13 stanzas of "Greensleeves".
- He has a son named Joseph born in 1997 with ex-wife Holly Aird.
- Voted "Hunk of the Year" by a British television magazine. (1997)
- At his Somerset home, Purefoy personally constructed a tree house for his young son.
- Lived with Fay Ripley for more than a decade.
- Moved out of his Hammersmith, London, home, which he shared with actress Holly Aird, and their son, Joseph. (May 2002)
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